Fibre-reactive azo dyestuffs containing a halo substituted pyrimidine substituent

ABSTRACT

Fiber-reactive monoazo and disazo compounds of the formula 
     
         D-N═N--K 
    
     which compounds are in free acid or salt form, and mixtures thereof, are useful for dyeing or printing hydroxy group- or nitrogen-containing organic substrates, for example leather and fiber material comprising natural or synthetic polyamides or natural or regenerated cellulose; the most preferred substrate is a textile material comprising cotton.

This is a continuation of application Ser. No. 08/135,038, filed Oct. 12, 1993, now abandoned.

This invention relates to fibre-reactive monoazo and disazo compounds and processes for their production. These compounds are suitable for use as fibre-reactive dyestuffs in any conventional dyeing or printing processes.

More particularly, the invention provides compounds of formula I

    D-N═N--K                                               I

and salts thereof, or a mixture of such compounds or salts, in which

D is one of the radicals (d₁) to (d₅), ##STR1## and K is one of the radicals (k₁) to (k₄); ##STR2## with the provisos that (i) a compound of formula I contains at least one sulphonic acid group;

(ii) a compound of formula I contains one or two radicals Y;

(iii) at least one of the radicals Y contains the radical ##STR3## and (iv) when D is (d₃) and K is (k₄), Y in (k₄) is other than ##STR4## or D is one of the radicals (d₁) to (d₄) above, or (d₆) or (d₇) of the formula ##STR5## and K is a radical (k₅) ##STR6## with the proviso that when D is (d₁) to (d₄), the same provisos (i) to (iv) as given above apply;

in which

each

Y is independently --NR₁ -Z_(a) or ##STR7## each Z_(a) is independently ##STR8## wherein T₁ is hydrogen, cyano or chloro, and the two T₂ 's are the same and each T₂ is fluoro or chloro;

each of

a and b is independently 0 or 1,

each

R₁ is independently hydrogen, C₁₋₄ alkyl or substituted C₁₋₄ alkyl,

Hal is fluoro or chloro,

W₁ is --NR₁ --B₁ --NR₁ --, ##STR9## in which the marked nitrogen atom is attached to a carbon atom of the triazine ring;

B1 is C₂₋₆ alkylene, --C₂₋₃ alkylene-Q-C₂₋₃ alkylene-, wherein Q is --O-- or --NR₁ --; C₃₋₄ alkylene monosubstituted by hydroxy, ##STR10## wherein the marked carbon atom is attached to the NR₁ -group which is bound to a carbon atom of the triazine ring;

R₂ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy or sulpho,

R₃ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen or carboxy,

each

R₄ is independently hydrogen or sulpho,

R₅ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy,

R₆ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, acetamido or --NHCONH₂,

R₇ is ##STR11## each R₈ is independently hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen or sulpho,

each

R₉ is independently hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen or carboxy,

R₁₀ is C₁₋₄ alkyl or --CH₂ SO₃ H,

R₁₁ is hydrogen; --CONH₂ ; sulpho; C₁₋₄ alkyl which is monosubstituted by hydroxy, halogen, cyano, C₁₋₄ alkoxy, sulpho, --OSO₃ H or --NH₂ ; or --CH₂ --Y,

R₁₂ is hydrogen; C₁₋₆ alkyl; substituted C₁₋₆ alkyl; cyclohexyl; phenyl or phenyl which is substituted by 1 to 3 substituents selected from halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, sulpho and carboxy; phenyl(C₁₋₄ alkyl) or phenyl(C₁₋₄ alkyl) the phenyl ring of which is substituted by 1 to 3 substituents selected from halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, sulpho and carboxy;

each

R₁₃ is hydroxy or --NH₂,

each

R₁₄ is C₁₋₄ alkyl, carboxy or --CONH₂,

R₁₅ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy,

R₁₆ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, acetamido or --NHCONH₂,

R₁₇ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, carboxy or sulpho, and

each

R₁₈ is independently hydrogen, halogen, C₁₋₄ alkyl or C₁₋₄ alkoxy;

X₁ is ##STR12## or wherein the marked carbon atom is bound to the azo group, and X₂ is ##STR13## wherein the marked carbon atom is attached to the Z_(a) -NR₁ -group;

m is 0 or 1,

n is 0 or an integer 1 to 4,

each

p is independently 0, 1 or 2,

each

q is independently 1 or 2,

each

r is 2 or 3, and

t is 1, 2 or 3.

In the specification, any alkyl, alkoxy or alkylene group present is linear or branched unless indicated otherwise. In any hydroxysubstituted alkyl or alkylene group which is attached to a nitrogen atom, the hydroxy group is preferably bound to a carbon atom which is not directly attached to the nitrogen atom. In any alkylene chain interrupted by Q which is attached to a nitrogen atom, Q is preferably bound to a carbon atom which is not directly attached to the nitrogen atom.

When R₁ is a substituted alkyl group, it is preferably monosubstituted by hydroxy, cyano or chloro.

Each R₁ is preferably R_(1a), where each R_(1a) is independently hydrogen, methyl, ethyl or 2-hydroxyethyl; more preferably each R₁ is R_(1b), where each R_(1b) is independently hydrogen or methyl. Most preferably each R₁ is hydrogen.

Any halogen as a phenyl substituent is preferably fluorine, chlorine or bromine; most preferably it is chlorine.

Hal is most preferably chlorine.

R₁₇ is preferably R_(17a), where R_(17a) is hydrogen, methyl, methoxy, carboxy or sulpho; more preferably it is R_(17b), where R_(17b) is hydrogen or sulpho.

B₁ is preferably B_(1a), where B_(1a) is C₂₋₃ alkylene, --CH₂ CH₂ --O--CH₂ CH₂ --, --CH₂ CH₂ --NR_(1b) --CH₂ CH₂ --, C₃₋₄ alkylene monosubstituted by hydroxy, ##STR14## in which n' is 0 or 1; more preferably it is B_(1b), where B_(1b) is C₂₋₃ alkylene, ##STR15## most preferably, it is B_(1c), where B_(1c) is --CH₂ CH₂ --, --CH₂ CH₂ CH₂ --, --*CH₂ CH(CH₃)-- or --CH₂ CH(OH)CH₂ -- in which the marked carbon atom is bound to the NR₁ -group which is attached to a carbon atom of the triazine ring.

W₁ is preferably W_(1a), where W_(1a) is --NR_(1a) --B_(1a) --NR_(1a) --, ##STR16## more preferably it is W_(1b), where W_(1b) is --NR_(1b) --B_(1b) --NR_(1b) -- or ##STR17## most preferably W₁ is W_(1c), where W_(1c) is --NH--B_(1c) --NH--.

Z_(a) is preferably Z_(a) ', where Z_(a) ' is ##STR18## in which T₁ ' is hydrogen or chloro; most preferably, Z_(a) is ##STR19##

Y is preferably Y_(a), where Y_(a) is --NR_(1b) -Z_(a) ' or ##STR20##

More preferably Y is Y_(b), where Y_(b) is ##STR21##

R₂ is preferably R_(2a), where R_(2a) is hydrogen, methyl, methoxy or sulpho.

R₃ is preferably R_(3a), where R_(3a) is hydrogen, methyl, methoxy, chloro or carboxy; more preferably, it is R_(3b), where R_(3b) is hydrogen, methyl or methoxy.

R₅ is preferably R_(5a), where R_(5a) is hydrogen, methyl or methoxy; most preferably, R₅ is hydrogen.

R₆ is preferably R_(6a), where R_(6a) is hydrogen, methyl, methoxy, acetamido or --NHCONH₂ ; more preferably, it is R_(6b), where R_(6b) is hydrogen, methyl, acetamido or --NHCONH₂.

R₈ is preferably R_(8a), where R_(8a) is hydrogen, methyl, methoxy, chloro or sulpho. Most preferably, R₈ is R_(8b), where R_(8b) is hydrogen, chloro or sulpho.

R₉ is preferably R_(9a), where R_(9a) is hydrogen, methyl, methoxy or chloro.

R₇ is preferably R_(7a) of the formula ##STR22## more preferably, R₇ is R_(7b) of the formula ##STR23##

R₁₀ is preferably R_(10a), where R_(10a) is methyl or --CH₂ SO₃ H.

R₁₁ is preferably R_(11a), where R_(11a) is hydrogen, --CONH₂, sulpho, --CH₂ SO₃ H or --CH₂ --Y_(a) ; more preferably, it is R_(11b), where R_(11b) is hydrogen, --CH₂ SO₃ H or --CH₂ --Y_(b).

Any substituted C₁₋₆ alkyl as R₁₂ is preferably --C₁₋₆ alkylene-E, in which E is carboxy, sulpho, --OSO₃ H, hydroxy, cyano, methoxy, --NR₁₉ R₂₀ or --.sup.⊕ NR₂₁ R₂₂ R₂₃ An.sup.⊖ wherein

each of

R₁₉ and R₂₀ is independently hydrogen, unsubstituted C₁₋₄ alkyl, C₁₋₄ alkyl monosubstituted by hydroxy, C₁₋₄ alkoxy, carboxy, sulpho, --NHC₁₋₄ alkyl or --N(C₁₋₄ alkyl)₂ ; cyclohexyl which is unsubstituted or substituted by one to three methyl groups; phenyl or phenyl which is substituted by 1 or 2 substituents selected from halogen, especially chloro, C₁₋₄ alkyl, C₁₋₄ alkoxy, sulpho and carboxy; phenyl(C₁₋₄ -alkyl) or phenyl-(C₁₋₄ alkyl) in which the phenyl ring is substituted by 1 or 2 substituents selected from halogen, especially chloro, C₁₋₄ alkyl, C₁₋₄ alkoxy, sulpho and carboxy; or

--NR₁₉ R₂₀ is piperidino, morpholino or piperazino in which the latter is unsubstituted or substituted by up to three methyl groups;

each of

R₂₁ and R₂₂ has one of the significances of R₁₉ and R₂₀ with the exception of hydrogen, but independent thereof; and R₂₃ is C₁₋₄ alkyl or benzyl, or

--.sup.⊕ NR₂₁ R₂₂ R₂₃ is a pyridinium ring which is further unsubstituted or substituted by 1 to 2 methyl groups, and

An.sup.⊖ is a non-chromophoric anion.

Preferably E is E_(a), where E_(a) is carboxy, sulpho, --OSO₃ H, hydroxy or --NR_(19a) R_(20a) wherein each of R_(19a) and R_(20a) is independently hydrogen, methyl, ethyl, 2-hydroxyethyl or phenyl(C₁₋₂ alkyl), or --NR_(19a) R_(20a) is piperidino, morpholino or piperazino.

More preferably, E is E_(b), where E_(b) is hydroxy, sulpho or --NR_(19b) R_(20b) wherein each of R_(19b) and R_(20b) is independently hydrogen, methyl or ethyl.

Any An.sup.⊖ is preferably a chloride or acetate ion.

R₁₂ is preferably R_(12a), where R_(12a) is hydrogen, methyl, ethyl, cyclohexyl, phenyl, phenyl(C₁₋₄ alkyl) or --C₁₋₆ alkylene-E; more preferably it is R_(12b), where R_(12b) is hydrogen, methyl, ethyl, cyclohexyl or --C₁₋₄ alkylene-E_(a) ; even more preferably it is R_(12c), where R_(12c) is hydrogen, methyl, ethyl or --C₁₋₃ alkylene-E_(b) ; most preferably, R₁₂ is R_(12d), where R_(12d) is hydrogen, methyl or ethyl.

R₁₃ is preferably hydroxy.

R₁₄ is preferably R_(14a), where R_(14a) is methyl or carboxy; most preferably R₁₄ is carboxy.

R₁₅ is preferably R_(15a), where R_(15a) is hydrogen, methyl or methoxy; most preferably R₁₅ is hydrogen.

R₁₆ is preferably R_(16a), where R_(16a) is hydrogen, methyl, methoxy, acetamido or --NHCONH₂ ; more preferably R_(16a) is R_(16b), where R_(16b) is hydrogen, methyl, acetamido or --NHCONH₂.

Each R₁₈ is preferably R_(18a), where each R_(18a) is independently hydrogen, chloro, methyl or methoxy. More preferably it is R_(18b), where each R_(18b) is independently hydrogen or methyl. Most preferably each R₁₈ is hydrogen.

X₁ is preferably X₁ ', where X₁ ' is ##STR24## in which the marked carbon atom is attached to the azo group. More preferably X₁ is X₁ ", where X₁ " is ##STR25## in which the marked carbon atom is attached to the azo group.

In X₂, q is preferably 1.

X₂ is preferably X₂ ', where X₂ ' is ##STR26## in which the marked carbon atom is attached to the Z_(a) -NR₁ -group. More preferably it is X₂ ", where X₂ " is ##STR27## in which the marked carbon atom is attached to the Z_(a) -NR₁ -group.

(d₁) is preferably (d₁ ') and more preferably (d₁ ") of the formulae ##STR28##

(d₂) is preferably (d₂ ') and more preferably (d₂ ") of the formulae ##STR29##

(d₃) is preferably (d₃ '), more preferably (d₃ ") in which the substituents are in the following positions: ##STR30## a) when the azo group is in the 1-position and r is 2, the sulpho groups are in the 3,6-; 3,8-; 4,6- or 4,8-positions; more preferably in the 3,6-positions;

b) when the azo group is in the 1-position and r is 3, the sulpho groups are in the 3,6,8-positions;

c) when the azo group is in the 2-position and r is 2, the sulpho groups are in the 1,5-; 3,6-; 4,8-; 5,7- or 6,8-positions; more preferably in the 1,5- or 4,8-positions;

d) when the azo group is in the 2-position and r is 3, the sulpho groups are in the 3,6,8- or 4,6,8-positions.

(d₄) is preferably (d₄ ') of the formula ##STR31## and most preferably (d₄ ") which is (d₄ ') wherein R_(5a) is hydrogen and R_(6a) is R_(6b) ; and where in each (d₄ ') and (d₄ ") the positions of the sulpho groups in the naphthyl ring related to the azo group are those as given for (d₃ ') and (d₃ "), respectively.

(d₅) is preferably (d₅ ') of the formula ##STR32## and more preferably (d₅ ") as (d₅ ') in which Y_(a) is Y_(b).

(d₆) is preferably (d₆ ') and more preferably (d₆ ") of the formulae ##STR33##

(d₇) is preferably (d₇ ') and more preferably (d₇ ") of the formulae ##STR34##

(k₁) is preferably (k₁ ') and more preferably (k₁ ") of the formulae ##STR35##

(k₂) is preferably (k₂ ') and more preferably (k₂ ") of the formulae ##STR36##

(k₃) is preferably (k₃ ') and more preferably (k₃ ") of the formulae ##STR37##

(k₄) is preferably (k₄ ') and more preferably (k₄ ") of the formulae ##STR38##

Preferred compounds of formula I correspond to formula Ia

    D.sub.a -N═N--K.sub.a                                  Ia

and salts thereof, in which D_(a) is one of the radicals (d₁ ') to (d₅ ') as defined above, and K_(a) is one of the radicals (k₁ ') to (k₄ ') as defined above, where the same provisos (i) to (iv) set forth for the compounds of formula I apply accordingly;

or to formula Ib ##STR39## and salts thereof, in which D_(b) is one of the radicals (d₁ ') to (d₄ ') or (d₆ ') or (d₇ ') and p' is 1 or 2, where in the case that two radicals Z_(a) ' are present, these are identical;

with the proviso that when D_(b) is one of the radicals (d₁ ') to (d₄ '),

at least one Z_(a) ' is ##STR40##

More preferred compounds of formula Ia are those in which D_(a) is D_(a) ', where D_(a) ' is one of the radicals (d₁ ") to (d₅ "), and K_(a) is K_(a) ', where K_(a) ' is one of the radicals (k₁ ") to (k₄ ").

More preferred compounds of formula Ib are those in which

(1) R_(18a) is R_(18b) and especially hydrogen;

(2) R_(14a) is carboxy;

(3) p' is 1;

(4) each R_(1b) is hydrogen; and

(5) in case where two groups Z_(a) ' are present, both Z_(a) ' are ##STR41##

Most preferred are compounds of formula Ic ##STR42## and salts thereof, in which D_(c) is (d₆ ") or (d₇ ") and in which the two groups Z_(a) ' are the same.

When a compound of formula I is in salt form, the cation associated with the sulpho groups and any carboxy group is not critical and may be any one of those non-chromophoric cations conventional in the field of fibre-reactive dyes provided that the corresponding salts are water-soluble. Examples of such cations are alkali metal cations and unsubstituted and substituted ammonium cations, e.g., lithium, sodium, potassium, ammonium, mono-, di-, tri- and tetra-methylammonium, tri-ethylammonium and mono-, di- and tri- ethanolammonium.

The preferred cations are the alkali metal cations and ammonium, with sodium being the most preferred.

In a compound of formula I the cations of the sulpho and any carboxy groups can be the same or different, e.g., they can also be a mixture of the above mentioned cations meaning that the compound of formula I can be in a mixed salt form.

The invention further provides a process for the preparation of compounds according to formula I or mixtures thereof, comprising reacting the diazonium salt of an amine of formula II,

    D-NH.sub.2                                                 II

in which D is as defined above,

with a compound of formula III,

    K--H                                                       III

in which K is as defined above.

It is also possible to use a compound of formula III in which instead of Z_(a) the free amino group --NR₁ --H is still present which, after the coupling reaction has been completed, may be reacted with a compound Z_(a) -Hal , wherein Hal is fluoro or chloro.

Compounds of formula I in which D is (d₆) or (d₇) and both Z_(a) are identical, preferably may be prepared by reacting 1 mole of a compound of formula IV ##STR43## in which D' is ##STR44## and R₁, R₁₃, R₁₄, R₁₈, p, X₁ and X₂ are as defined above, with at least 2 moles of a compound Z_(a) -Hal in which Z_(a) is as defined above and Hal is fluoro or chloro.

Diazotisation and coupling may be carried out in accordance with conventional methods; the pH of the coupling reaction has to be adapted in accordance with each different coupling component used.

The condensation of an amino group with a compound Z_(a) -Hal is suitably carried out at a slightly elevated temperature in the range of from 20°-60° C., and at a pH of 4-7.

The compounds of formula I may be isolated in accordance with known methods, for example, by conventional salting out with alkali metal salt, filtering and drying optionally in vacuo and at slightly elevated temperatures.

Depending on the reaction and isolation conditions a compound of formula I is obtained in free acid or preferably salt form or even mixed salt form containing, for example, one or more of the above mentioned cations. It may be converted from free acid form to a salt form or mixture of salt forms or vice versa or from one salt form to another by conventional means.

It should be noted that any group Z_(a) corresponding to the formula ##STR45## in which T₁ is hydrogen, cyano or chloro and T₂ is fluoro or chloro, can occur in two isomeric forms, with the floating fluoro or chloro substituent in either the 2- or the 6-position.

In general, it is preferred to use this mixture of resulting dyestuffs as it is without resorting to the isolation of a single isomer for use, but should this be desired it can be readily achieved by conventional methods.

The starting compounds of formulae II, III and IV as well as Z_(a) -Hal are either known or may be readily made from known starting materials by known methods.

The compounds of formula I and mixtures thereof are useful as fibre-reactive dyestuffs for dyeing or printing hydroxy group- or nitrogen-containing organic substrates. Preferred substrates are leather and fibre material comprising natural or synthetic polyamides and, particularly, natural or regenerated cellulose such as cotton, viscose and spun rayon. The most preferred substrate is textile material comprising cotton.

Dyeing or printing is effected in accordance with known methods conventional in the fibre-reactive dyestuff field. Preferably, for the compounds of formula I the exhaust dyeing method is used at temperatures within the range of from 30° to 80° C., particularly at 50°-60° C., whereby a liquor to goods ratio of 6:1 to 30:1 is used and more preferably of 10:1 to 20:1.

The compounds of this invention have good compatibility with known fibre-reactive dyes; they may be applied alone or in combination with appropriate fibre-reactive dyestuffs of the same class having analogous dyeing properties such as common fastness properties and the extent of ability to exhaust from the dyebath onto the fibre. The dyeings obtained with such combination mixtures have good fastness properties and are comparable to those obtained with a single dyestuff.

The compounds of formula I give good exhaust and fixation yields when used as dyestuffs. Moreover, any unfixed compound is easily washed off the substrate. The dyeings and prints derived from the compounds of formula I exhibit good light fastness and good wet fastness properties such as wash water, sea water and sweat fastness. They also exhibit good resistance to oxidation agents such as chlorinated water, hypochlorite bleach, peroxide bleach and perborate-containing washing detergents.

The following examples illustrate the invention. In the examples all parts and percentages are by weight unless indicated to the contrary, and all temperatures are given in degrees Centigrade.

EXAMPLE 1

63.1 Parts of the compound of the formula ##STR46## are stirred into 600 parts of water and 38 parts by volume of an aqueous 4N sodium nitrite solution are added thereto. The suspension thus obtained is added dropwise to a mixture of 45 parts of 30% hydrochloric acid and 300 parts of ice at 0°-5° and within 50 minutes. Stirring is effected for one further hour and after this the excess nitrite is decomposed by adding a small amount of sulphamic acid. Subsequently, 4.5 parts of 1-ethyl-6-hydroxy-4-methyl-3-sulphomethylpyridone(-2) dissolved in 500 parts of water, are added thereto, and afterwards the pH is adjusted to 7.0 by the addition of 320 parts by volume of 20% sodium carbonate solution. After coupling is complete, the dyestuff is precipitated from the yellow suspension obtained by adding 450 parts of sodium chloride, it is filtered off and dried. The dyestuff corresponds to the formula (shown in free acid form) ##STR47## it dyes cotton in greenish yellow shades. These dyeings exhibit good fastness properties and are resistant to oxidative influences.

EXAMPLES 2-124

By analogy with the method described in Example 1, using appropriate starting compounds, further compounds of formula I can be prepared which are listed in the following Tables 1 to 3. They correspond to the formula (T)

    A-N═N--B                                               (T)

in which the significances of each A and B are set forth in Tables 1-3.

In addition, the following symbols are used:

Z₁ for ##STR48## Z₄ for ##STR49## Z₂ for ##STR50## Z₅ for ##STR51## Z₃ for ##STR52## Z₆ for ##STR53## in Table 1, under column A D₁ is ##STR54## and D₂ is ##STR55## and in Table 2, under column A D₃ is ##STR56## in which the symbols are as defined in Tables 1 and 2, respectively.

The compounds of Examples 2 to 124 may be applied to substrates which comprise cellulose fibres, and particularly to textile material comprising cotton using the conventional exhaust dyeing method or conventional printing processes, where dyeings or prints in greenish yellow to golden yellow shades are obtained. These dyeings and prints on cotton show good properties with respect to light fastness and wet fastnesses and are resistant to oxidative influences.

    TABLE 1                                                                           - Example 2-64                                                                  Ex. No. A R Z.sub.x R.sub.1 Hal W.sub.1                                          B                                                                              2                                                                              ##STR57##                                                                        -- Z.sub.1 H -- --                                                              ##STR58##                                                                       3 D.sub.2                                                                      ##STR59##                                                                        " H -- -- "                                                                     4 " " " CH.sub.3 -- -- "                                                        5 "                                                                            ##STR60##                                                                        " H -- -- "                                                                     6 D.sub.1 " -- H -- --                                                         ##STR61##                                                                        7                                                                              ##STR62##                                                                        -- -- H -- -- "                                                                 8                                                                              ##STR63##                                                                        -- -- CH.sub.3 -- -- "                                                          9                                                                              ##STR64##                                                                        -- -- H Cl                                                                      ##STR65##                                                                       ##STR66##                                                                      10                                                                               ##STR67##                                                                       -- -- H Cl " "                                                                 11 " -- -- H F " "                                                              12 D.sub.1                                                                       ##STR68##                                                                       -- H Cl NHCH.sub.2 CH.sub.2                                                     NH                                                                             ##STR69##                                                                       13                                                                               ##STR70##                                                                       -- Z.sub.4 H Cl                                                                 ##STR71##                                                                       ##STR72##                                                                      14 D.sub.2                                                                       ##STR73##                                                                       " H Cl                                                                          ##STR74##                                                                       "                                                                              15 " " " H F " "                                                                16 D.sub.2                                                                       ##STR75##                                                                       Z.sub.4 H Cl                                                                    ##STR76##                                                                       ##STR77##                                                                      17 " " " H F " "                                                                18                                                                               ##STR78##                                                                       -- Z.sub.1 H -- --                                                              ##STR79##                                                                      19 D.sub.2                                                                       ##STR80##                                                                       Z.sub.1 H -- --                                                                 ##STR81##                                                                      20                                                                               ##STR82##                                                                       -- -- H -- --                                                                   ##STR83##                                                                      21                                                                               ##STR84##                                                                       -- -- H -- -- "                                                                22                                                                               ##STR85##                                                                       -- -- CH.sub.3 -- --                                                            ##STR86##                                                                      23 D.sub.1                                                                       ##STR87##                                                                       -- H Cl                                                                         ##STR88##                                                                       ##STR89##                                                                      24                                                                               ##STR90##                                                                       -- -- H Cl " "                                                                 25 D.sub.2                                                                       ##STR91##                                                                       Z.sub.1 H -- --                                                                 ##STR92##                                                                      26                                                                               ##STR93##                                                                       -- " H -- -- "                                                                 27 " -- " H -- --                                                                ##STR94##                                                                      28 " -- " H -- --                                                                ##STR95##                                                                      29                                                                               ##STR96##                                                                       -- Z.sub.4 H Cl                                                                 ##STR97##                                                                       ##STR98##                                                                      30 " -- " H F " "                                                               31 " -- " CH.sub.3 Cl                                                            ##STR99##                                                                       "                                                                              32                                                                               ##STR100##                                                                      -- Z.sub.4 H Cl                                                                 ##STR101##                                                                      ##STR102##                                                                     33 " -- " CH.sub.3 Cl " "                                                        34 " -- " H F " "                                                              35 " -- " H Cl                                                                   ##STR103##                                                                      "                                                                              36 D.sub.2                                                                       ##STR104##                                                                      Z.sub.4 H Cl                                                                    ##STR105##                                                                      ##STR106##                                                                     37 " " " CH.sub.3 Cl                                                             ##STR107##                                                                      "                                                                              38 D.sub.1                                                                       ##STR108##                                                                      -- H -- --                                                                      ##STR109##                                                                     39                                                                               ##STR110##                                                                      -- -- CH.sub.3 -- -- "                                                         40                                                                               ##STR111##                                                                      -- -- H -- -- "                                                                41                                                                               ##STR112##                                                                      -- -- H -- -- "                                                                42                                                                               ##STR113##                                                                      -- Z.sub.1 H -- --                                                              ##STR114##                                                                     43                                                                               ##STR115##                                                                      -- " H -- -- "                                                                 44                                                                               ##STR116##                                                                      -- " H -- --                                                                    ##STR117##                                                                     45 D.sub.2                                                                       ##STR118##                                                                      " H -- -- "                                                                    46                                                                               ##STR119##                                                                      -- " H -- --                                                                    ##STR120##                                                                     47                                                                               ##STR121##                                                                      -- " H -- --                                                                    ##STR122##                                                                     48 D.sub.2                                                                       ##STR123##                                                                      Z.sub.4 H Cl                                                                    ##STR124##                                                                      "                                                                              49                                                                               ##STR125##                                                                      -- " H Cl NHCH.sub.2 CH.sub.2 CH.sub.2                                          NH                                                                             ##STR126##                                                                      50 D.sub.2                                                                       ##STR127##                                                                      Z.sub.1 H -- -- "                                                              51 D.sub.1                                                                       ##STR128##                                                                      -- H Cl                                                                         ##STR129##                                                                      ##STR130##                                                                     52                                                                               ##STR131##                                                                      -- -- CH.sub.3 Cl " "                                                          53                                                                               ##STR132##                                                                      -- -- H -- --                                                                   ##STR133##                                                                     54                                                                               ##STR134##                                                                      -- -- H -- -- "                                                                55 D.sub.1                                                                       ##STR135##                                                                      -- H Cl                                                                         ##STR136##                                                                      ##STR137##                                                                     56 " " -- H F " "                                                               57                                                                               ##STR138##                                                                      -- -- CH.sub.3 -- --                                                            ##STR139##                                                                     58                                                                               ##STR140##                                                                      -- -- H -- -- "                                                                59 D.sub.1                                                                       ##STR141##                                                                      -- H -- -- "                                                                   60 " " -- CH.sub.3 -- --                                                         ##STR142##                                                                     61                                                                               ##STR143##                                                                      -- -- H Cl                                                                      ##STR144##                                                                      ##STR145##                                                                     62                                                                               ##STR146##                                                                      -- -- H Cl                                                                      ##STR147##                                                                      ##STR148##                                                                     63 " -- -- H Cl                                                                  ##STR149##                                                                      "                                                                              64 " -- -- H F " "                                                        

    TABLE 2                                                                           - Examples 65-                                                                  101                                                       Ex.  optionall       y                                                                                No. A with R.sub.x R.sub.5 R.sub.6 R.sub.1 Hal W.sub.1                           B                                                                              65 D.sub.3                                                                      ##STR150##                                                                      H NHCONH.sub.2 H " "                                                            ##STR151##                                                                     66 D.sub.3                                                                       ##STR152##                                                                      H " H -- --                                                                     ##STR153##                                                                     67 " " H NHCOCH.sub.3 CH.sub.3 -- -- "                                          68 "                                                                             ##STR154##                                                                      OCH.sub.3 CH.sub.3 H -- --                                                      ##STR155##                                                                      69                                                                              ##STR156##                                                                      -- -- H -- --                                                                   ##STR157##                                                                     70 " -- -- H -- --                                                               ##STR158##                                                                     71                                                                               ##STR159##                                                                      -- -- H -- --                                                                   ##STR160##                                                                     72                                                                               ##STR161##                                                                      -- -- H Cl                                                                      ##STR162##                                                                      ##STR163##                                                                     73 " -- -- H Cl                                                                  ##STR164##                                                                      "                                                                              74 " -- ' H F " "                                                               75                                                                               ##STR165##                                                                      -- -- H -- --                                                                   ##STR166##                                                                     76                                                                               ##STR167##                                                                      -- -- H -- --                                                                   ##STR168##                                                                     77 " -- -- H -- --                                                               ##STR169##                                                                     78                                                                               ##STR170##                                                                      -- -- H Cl                                                                      ##STR171##                                                                      ##STR172##                                                                     79                                                                               ##STR173##                                                                      -- -- H Cl                                                                      ##STR174##                                                                      ##STR175##                                                                     80 " -- -- H Cl                                                                  ##STR176##                                                                     81 " -- -- CH.sub.3 Cl " "                                                       82 " -- -- H F " "                                                              83 D.sub.3                                                                      ##STR177##                                                                      H H H -- --                                                                     ##STR178##                                                                     84 " " H NHCOCH.sub.3 H CL NHCH.sub.2 CH.sub.2                                   NH                                                                             ##STR179##                                                                      85 " " OCH.sub.3 H H Cl                                                          ##STR180##                                                                      "                                                                              86 " " " CH.sub.3 H F " "                                                       87 "                                                                             ##STR181##                                                                      H NHCONH.sub.2 H -- --                                                          ##STR182##                                                                     88 D.sub.3                                                                       ##STR183##                                                                      H CH.sub.3 H -- --                                                              ##STR184##                                                                     89 "                                                                             ##STR185##                                                                      H H CH.sub.3 -- --                                                              ##STR186##                                                                     90 "                                                                             ##STR187##                                                                      OCH.sub.3 CH.sub.3 H Cl                                                         ##STR188##                                                                      ##STR189##                                                                     91 " " " " H F                                                                   ##STR190##                                                                      "                                                                              92 "                                                                             ##STR191##                                                                      H NHCOCH.sub.3 H Cl                                                             ##STR192##                                                                      ##STR193##                                                                     93 "                                                                             ##STR194##                                                                      H NHCONH.sub.2 H -- --                                                          ##STR195##                                                                      94                                                                              ##STR196##                                                                      -- -- H -- --                                                                   ##STR197##                                                                     95                                                                               ##STR198##                                                                      -- -- H -- --                                                                   ##STR199##                                                                     96                                                                               ##STR200##                                                                      -- -- H -- --                                                                   ##STR201##                                                                     97                                                                               ##STR202##                                                                      -- -- H Cl                                                                      ##STR203##                                                                      ##STR204##                                                                      98 D.sub.3                                                                      ##STR205##                                                                      H H H -- --                                                                     ##STR206##                                                                     99 "                                                                             ##STR207##                                                                      H NHCOCH.sub.3 H Cl NHCH.sub.2 CH.sub.2 CH.sub.2                                NH                                                                             ##STR208##                                                                      100                                                                               " " H " H F " "                                                                 101                                                                             "                                                                             ##STR209##                                                                       CH.sub.3 CH.sub.3 H -- --                                                       ##STR210##                                                               

                                      TABLE 3                                      __________________________________________________________________________     Examples 102- 124                                                              Ex. No.                                                                            A                     R.sub.1                                                                          Hal                                                                               W.sub.1    B                                    __________________________________________________________________________     102                                                                                 ##STR211##           H -- --                                                                                          ##STR212##                         103                                                                                 ##STR213##           H -- --                                                                                          ##STR214##                         104                                                                                 ##STR215##           H -- --                                                                                          ##STR216##                         105                                                                                 ##STR217##           H Cl                                                                                 ##STR218## "                                   106                                                                                 ##STR219##           H Cl "                                                                                           ##STR220##                         107 "                     H F  "           "                                   108 "                     H -- --                                                                                          ##STR221##                         109                                                                                 ##STR222##           H -- --          "                                   110                                                                                 ##STR223##           H -- --          "                                   111                                                                                 ##STR224##           H Cl                                                                                 ##STR225##                                                                                 ##STR226##                         112                                                                                 ##STR227##           H Cl "           "                                   113                                                                                 ##STR228##           H -- --          "                                   114                                                                                 ##STR229##           H -- --                                                                                          ##STR230##                         115                                                                                 ##STR231##           H -- --          "                                   116                                                                                 ##STR232##           H Cl                                                                                 ##STR233##                                                                                 ##STR234##                         117 "                     H -- --                                                                                          ##STR235##                         118                                                                                 ##STR236##           H Cl NHCH.sub.2 CH.sub.2 CH.sub.2 NH                                                             ##STR237##                         119                                                                                 ##STR238##           H Cl "                                                                                           ##STR239##                         120 "                     H F                                                                                  ##STR240##                                                                                 ##STR241##                         121                                                                                 ##STR242##           H -- --                                                                                          ##STR243##                         122 "                     H -- --                                                                                          ##STR244##                         123                                                                                 ##STR245##           H -- --                                                                                          ##STR246##                         124                                                                                 ##STR247##           H Cl                                                                                 ##STR248## "                                   __________________________________________________________________________

EXAMPLE 125

160 Parts of the diaminoazo compound of the formula ##STR249## which has been prepared in accordance with a conventional method, are dissolved in 2000 parts of water. At 25°-30°, 37.1 parts of 2,4,6-trifluoro-5-chloropyrimidine are added dropwise to this solution. During the addition, the pH of the reaction mixture is kept at 5.0 to 6.0 by continuous addition of 15% sodium carbonate solution. After the condensation is complete, the resultant dyestuff is precipitated with sodium chloride, filtered off and dried in vacuo at 50°. The dyestuff corresponds to the formula (shown in free acid form); ##STR250## it dyes cellulose material and especially cotton a yellow shade. These dyeings exhibit high fastness properties.

EXAMPLE 126

160 Parts of the diaminoazo compound of formula (la) described in Example 125, are dissolved in 2000 parts of water. To this solution 29.5 parts of 2,4,6-trifluoropyrimidine are added and stirring is effected at 40°-45°, until any free amino group is no longer detectable. Simultaneously, the acid set free during the reaction is buffered to a pH of 6-7 by continuously adding 15% sodium carbonate solution. The resultant dyestuff which corresponds to the formula (shown in free acid form) ##STR251## is precipitated with sodium chloride, filtered off and dried in vacuo at 50°. With this dyestuff yellow dyeings and prints on cotton are obtained which exhibit good general fastness properties and are resistant to oxidative influences.

EXAMPLES 127-219

By analogy with the method described in Example 125 and 126, using appropriate starting compounds, further compounds of formula I can be prepared which are listed in the following Tables 4 and 5. These compounds correspond to the formulae (T4) and (T5), where each formula is set forth on the top of the corresponding Table in which the symbols are defined.

In Table 4, under column X, the marked carbon atom is bound to the Z-NH-group of formula (T4); and in Table 5, under column X, the marked carbon atom is bound to the azo group of formula (T5).

Furthermore, in Tables 4 and 5 the following symbols are used:

Z₁ ' for ##STR252## Z₂ ' for ##STR253## and Z₃ ' for ##STR254##

With the dyestuffs of Examples 127 to 219 yellow dyeings on cotton are obtained which exhibit good light- and wet-fastness properties.

                                      TABLE 4                                      __________________________________________________________________________     Examples 127-183 compounds of formula (T4)                                      ##STR255##                                                                                             position of                                                                              position of                                 Ex. No.                                                                            X                    NN in ring A                                                                             NH in ring B                                                                            Z                                  __________________________________________________________________________     127                                                                                 ##STR256##          4         4        Z.sub.1 '                          128 "                    4         4        Z.sub.2 '                          129 "                    4         4        Z.sub.3 '                          130 "                    4         5        Z.sub.3 '                          131 "                    3         4        Z.sub.1 '                          132 "                    3         4        Z.sub.2 '                          133 "                    3         4        Z.sub.3 '                          134 "                    3         5        Z.sub.2 '                          135 "                    3         5        Z.sub.1 '                          136                                                                                 ##STR257##          4         4        Z.sub.1 '                          137 "                    4         4        Z.sub.2 '                          138 "                    4         4        Z.sub.3 '                          139 "                    3         4        Z.sub.1 '                          140 "                    3         4        Z.sub.2 '                          141 "                    3         5        Z.sub.1 '                          142 "                    3         5        Z.sub.2 '                          143 "                    4         5        Z.sub.1 '                          144 "                    4         5        Z.sub.2 '                          145                                                                                 ##STR258##          4         5        Z.sub.1 '                          146 "                    4         5        Z.sub.2 '                          147 "                    4         4        Z.sub.1 '                          148 "                    4         4        Z.sub.2 '                          149 "                    4         4        Z.sub.3 '                          150 "                    3         4        Z.sub.1 '                          151 "                    3         4        Z.sub.2 '                          152                                                                                 ##STR259##          3         5        Z.sub.1 '                          153 "                    3         5        Z.sub.2 '                          154 "                    3         5        Z.sub.3 '                          155                                                                                 ##STR260##          3         5        Z.sub.1 '                          156 "                    3         5        Z.sub.2 '                          157 "                    4         5        Z.sub.1 '                          158 "                    4         4        Z.sub.1 '                          159 "                    3         4        Z.sub.1 '                          160                                                                                 ##STR261##          4         4        Z.sub.1 '                          161 "                    4         5        Z.sub.1 '                          162 "                    3         4        Z.sub.1 '                          163 "                    3         4        Z.sub.2 '                          164 "                    3         5        Z.sub.1 '                          165                                                                                 ##STR262##          3         5        Z.sub.1 '                          166 "                    3         5        Z.sub.3 '                          167 "                    3         4        Z.sub.1 '                          168 "                    4         4        Z.sub.1 '                          169 "                    4         4        Z.sub.2 '                          170 "                    4         5        Z.sub.1 '                          171                                                                                 ##STR263##          4         5        Z.sub.1 '                          172 "                    4         5        Z.sub.2 '                          173 "                    4         4        Z.sub.2 '                          174 "                    3         4        Z.sub.1 '                          175 "                    3         4        Z.sub.2 '                          176 "                    3         5        Z.sub.1 '                          177 "                    3         5        Z.sub.2 '                          178                                                                                 ##STR264##          3         5        Z.sub.1 '                          179 "                    3         5        Z.sub.2 '                          180 "                    3         4        Z.sub.1 '                          181 "                    4         4        Z.sub.1 '                          182 "                    4         4        Z.sub.3 '                          183 "                    4         5        Z.sub.1 '                          __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________     Examples 184-219 compounds of formula (T5)                                      ##STR265##                                                                                             position of                                                                              position of                                 Ex. No.                                                                            X                    N═N in ring A                                                                        NH in ring B                                                                            Z                                  __________________________________________________________________________     184                                                                                 ##STR266##          4         4        Z.sub.1 '                          185 "                    4         4        Z.sub.2 '                          186 "                    4         4        Z.sub.3 '                          187 "                    4         5        Z.sub.3 '                          188 "                    3         4        Z.sub.1 '                          189 "                    3         4        Z.sub.2 '                          190                                                                                 ##STR267##          4         4        Z.sub.1 '                          191 "                    3         4        Z.sub.2 '                          192 "                    3         5        Z.sub.1 '                          193                                                                                 ##STR268##          3         5        Z.sub.1 '                          194 "                    3         5        Z.sub.2 '                          195 "                    3         4        Z.sub.1 '                          196 "                    4         5        Z.sub.1 '                          197 "                    4         4        Z.sub.1 '                          198 "                    4         4        Z.sub.2 '                          199 "                    4         4        Z.sub.3 '                          200                                                                                 ##STR269##          4         5        Z.sub.1 '                          201 "                    4         5        Z.sub.2 '                          202 "                    4         4        Z.sub.1 '                          203 "                    4         4        Z.sub.2 '                          204 "                    4         4        Z.sub.3 '                          205 "                    3         4        Z.sub.1 '                          206 "                    3         4        Z.sub.2 '                          207 "                    3         5        Z.sub.1 '                          208 "                    3         5        Z.sub.2 '                          209 "                    3         5        Z.sub.3 '                          210                                                                                 ##STR270##          3         5        Z.sub.1 '                          211 "                    3         5        Z.sub.2 '                          212 "                    4         5        Z.sub.1 '                          213 "                    4         4        Z.sub.1 '                          214 "                    3         4        Z.sub.1 '                          215                                                                                 ##STR271##          4         4        Z.sub.1 '                          216 "                    4         5        Z.sub.1 '                          217 "                    3         4        Z.sub.1 '                          218 "                    3         4        Z.sub.2 '                          219 "                    3         5        Z.sub.1,                           __________________________________________________________________________

By the preparation method described in Example 1, 125 or 126, the compounds of Examples 1-219 are obtained in their sodium salt form. By changing the reaction or isolation conditions or by using other known methods, it is possible to produce the compounds in the form of free acid or in other salt forms or mixed salt forms which contain one or more of the cations mentioned hereinabove.

As already mentioned hereinbefore in the description, the exemplified dyestuffs (and the corresponding free acids and other salt forms) contain two isomeric compounds regarding the radical ##STR272## one compound in which the floating fluoro- or chloro-substituent on the pyrimidine ring is in the 2-position and the corresponding compound wherein it is in the 6-position.

The obtained mixtures of isomeric dyestuffs may be used in conventional dyeing or printing processes; the isolation of a single isomer for use normally is unnecessary.

In the following examples, the application of the compounds of this invention is illustrated.

APPLICATION EXAMPLE A

0.3 Part of the dyestuff of Example 1 or 125 is dissolved in 100 parts of demineralised water and 8 parts of Glauber's salt (calcined) are added. The dyebath is heated to 50°, then 10 parts of cotton fabric (bleached) are added. After 30 minutes at 50°, 0.4 part of sodium carbonate (calcined) is added to the bath. During the addition of sodium carbonate the temperature is kept at 50°. Subsequently, the dyebath is heated to 600, and dyeing is effected for a further one hour at 60°.

The dyed fabric is then rinsed with running cold water for 3 minutes and afterwards with running hot water for a further 3 minutes. The dyeing is washed at the boil for 15 minutes in 500 parts of demineralised water in the presence of 0.25 part of Marseille soaps. After being rinsed with running hot water (for 3 minutes) and centrifuged, the dyeing is dried in a cabinet dryer at about 70°. A greenish yellow (yellow) cotton dyeing is obtained showing good fastness properties, and particularly high light- and wet-fastness properties, which is stable towards oxidative influences.

APPLICATION EXAMPLE B

To a dyebath containing in 100 parts of demineralised water 5 parts of Glauber's salt (calcined), 10 parts of cotton fabric (bleached) are added. The bath is heated to 50° within 10 minutes, and 0.5 part of the dyestuff of Example 1 or 125 is added. After a further 30 minutes at 50°, 1 part of sodium carbonate (calcined) is added. The dyebath is then heated to 60° and dyeing is continued at 60° for a further 45 minutes.

The dyed fabric is rinsed with running cold and then hot water and washed at the boil according to the method given in Application Example A. After rinsing and drying a greenish yellow (yellow) cotton dyeing is obtained which has the same good fastness properties as indicated in Application Example A.

Similarly, the dyestuffs of Examples 2-124 and 126 to 219 or mixtures of the exemplified dyestuffs may be employed to dye cotton in accordance with the method described in Application Example A or B. The cotton dyeings thus obtained are greenish yellow to golden yellow and show good fastness properties.

APPLICATION EXAMPLE C

A printing paste consisting of

    ______________________________________                                         40 parts    of the dyestuff of Example 1 or 125                                100 parts   of urea                                                            350 parts   of water                                                           500 parts   of a 4% sodium alginate thickener and                              10 parts    of sodium bicarbonate                                              1000 parts  in all                                                             ______________________________________                                    

is applied to cotton fabric in accordance with conventional printing methods.

The printed fabric is dried and fixed in steam at 102°-104° for 4-8 minutes. It is rinsed in cold and then hot water, washed at the boil (according to the method described in Application Example A) and dried. A greenish yellow (yellow) print is obtained which has good general fastness properties.

Similarly, the dyestuffs of Examples 2 to 124 and 126 to 219 or mixtures of the exemplified dyestuffs may be employed to print cotton in accordance with the method given in Application Example C. All prints obtained are greenish yellow to golden yellow and show good fastness properties. 

What is claimed is:
 1. A compound of formula I

    D-N═N--K                                               I

or salts thereof, or a mixture of such compounds or salts, in which D is one of the radicals (d₂) to (d₅), ##STR273## and K is one of the radicals (k₁) to (k₄); ##STR274## with the provisos that (i) a compound of formula I contains at least one sulphonic acid group; (ii) a compound of formula I contains one or two radicals Y; (iii) at least one of the radicals Y contains the radical ##STR275## (iv) when D is (d₃) and K is (k₄), Y in (k₄) is other than ##STR276## and (v) when D is (d₄) and K is (k₄); neither R₁₅ nor R₁₆ is hydrogen;or D is one of the radicals (d₂) or to (d₄) above, or (d₆) or (d₇) of the formula ##STR277## and K is a radical (k₅) ##STR278## with the proviso that when D is (d₂) or to (d₄), the same provisos (i) to (iv) as given above apply;in which each Y is independently --NR₁ -Z_(a) or ##STR279## each Z_(a) is independently ##STR280## wherein T₁ is hydrogen, cyano or chloro, and the two T₂ 's are the same and each T₂ is fluoro or chloro;each of a and b is independently 0 or 1,each R₁ is independently hydrogen, C₁₋₄ alkyl or substituted C₁₋₄ alkyl, Hal is fluoro or chloro, W₁ is --NR₁ --B₁ --NR₁ --, ##STR281## in which the marked nitrogen atom is attached to a carbon atom of the triazine ring; B₁ is C2-6alkylene, --C₂₋₃ alkylene-Q-C₂₋₃ alkylene-, wherein Q is --O-- or --NR₁ --; C₃₋₄ alkylene monosubstituted by hydroxy, ##STR282## wherein the marked carbon atom is attached to the NR₁ -group which is bound to a carbon atom of the triazine ring; R₄ is independently hydrogen or sulpho, R₅ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₆ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, acetamido or --NHCONH₂, R₇ is ##STR283## each R₈ is independently hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen or sulpho,each R₉ is independently hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, halogen or carboxy, R₁₀ is C₁₋₄ alkyl or --CH₂ SO₃ H, R₁₁ is hydrogen; --CONH₂ ; sulpho; C₁₋₄ alkyl which is monosubstituted by hydroxy, halogen, cyano, C₁₋₄ alkoxy, sulpho, --OSO₃ H or --NH2; or --CH₂ --Y, R₁₂ is hydrogen; C₁₋₄ alkyl; substituted C₁₋₆ alkyl; cyclohexyl; phenyl or phenyl which is substituted by 1 to 3 substituents selected from halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, sulpho and carboxy; phenyl(C₁₋₄ alkyl) or phenyl(C₁₋₄ alkyl) the phenyl ring of which is substituted by 1 to 3 substituents selected from halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, sulpho and carboxy;each R₁₃ is hydroxy or --NH₂,each R₁₄ is C₁₋₄ alkyl, carboxy or --CONH₂, R₁₅ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy, R₁₆ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, acetamido or --NHCONH₂, R₁₇ is hydrogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, carboxy or sulpho, andeach R₁₈ is independently hydrogen, halogen, C₁₋₄ alkyl or C₁₋₄ alkoxy; X₁ is ##STR284## wherein the marked carbon atom is bound to the azo group, and X₂ is ##STR285## wherein the marked carbon atom is attached to the Z_(a) -NR₁ -group; m is 0 or 1, n is 0 or an integer 1 to 4,each p is independently 0, 1 or 2,each q is independently 1 or 2,each r is 2 or 3, and t is 1, 2 or
 3. 2. A compound according to claim 1 in which Y is Y_(b), where Y_(b) is ##STR286## wherein W_(1c) is --NH--B_(1c) --NH-- in whichB_(1c) is --CH₂ CH₂ --, --CH₂ CH₂ CH₂ --, --*CH₂ CH(CH₃)-- or --CH₂ CH(OH)CH₂ -- and the marked carbon atom is bound to the --NH-group which is attached to a carbon atom of the triazine ring.
 3. A compound according to claim 2, in which R₅ is hydrogen, methyl or methoxy, and R₆ is hydrogen, methyl, methoxy, acetamido or --NHCONH₂.
 4. A compound according to claim 2, in which R₈ is hydrogen, methyl, methoxy, chloro or sulpho, and R₉ is hydrogen, methyl, methoxy or chloro.
 5. A compound according to claim 2, in which R₁₀ is methyl or --CH₂ SO₃ H; R₁₁ is hydrogen, --CH₂ SO₃ H or --CH₂ --Y_(b), in which Y_(b) is as defined in claim 2; and R₁₂ is hydrogen, methyl, ethyl, cyclohexyl or --C₁₋₄ alkylene-E_(a), wherein E_(a) is carboxy, sulpho, --OSO₃ H, hydroxy or --NR_(19a) R_(20a) and each of R_(19a) and R_(20a) is independently hydrogen, methyl, ethyl, 2-hydroxyethyl or phenyl(C₁₋₂ alkyl), or --NR_(19a) R_(20a) is piperidino, morpholino or piperazino.
 6. A compound according to claim 2, in which R₁₈ is hydrogen, chloro, methyl or methoxy.
 7. A compound according to claim 6, in which X₁ is ##STR287## wherein the marked carbon atom is attached to the azo group.
 8. A compound according to claim 6, in which X₂ is ##STR288## in which the marked carbon atom is bound to the Z_(a) -NR₁ -group.
 9. A compound according to claim 1, which corresponds to formula Ia

    D.sub.a -N═N--K.sub.a                                  Ia

or salts thereof, in which D_(a) is one of the radicals (d₂ ') to (d₅ '), ##STR289## wherein q is 1 or 2, a is 0 or 1, andeach Y_(a) is --NR_(1b) --Z_(a) ' or ##STR290## in which each R_(1b) is independently hydrogen or methyl, Hal is fluoro or chloro, W_(1b) is --NR_(1b) --B_(1b) --NR_(1b) -- or ##STR291## wherein B_(1b) is linear or branched C₂₋₃ alkylene, --CH₂ CH(OH)CH₂ -- or ##STR292## and R_(17b) is hydrogen or sulpho; and Z_(a) ' is ##STR293## wherein T₁ ' is hydrogen or chloro; ##STR294## in which r is 2 or 3 and the substituents are in the following positions: a) when the azo group is in the 1-position and r is 2, the sulpho groups are in the 3,6-; 3,8-; 4,6- or 4,8-positions; b) when the azo group is in the 1-position and r is 3, the sulpho groups are in the 3,6,8-positions; c) when the azo group is in the 2-position and r is 2, the sulpho groups are in the 1,5-; 3,6-; 4,8-; 5,7- or 6,8-positions; d) when the azo group is in the 2-position and r is 3, the sulpho groups are in the 3,6,8- or 4,6,8-positions; ##STR295## in which r is 2 or 3 and the sulpho groups in the naphthyl ring are in the same positions as shown for (d₃ ') above, R₅ a is hydrogen, methyl or methoxy, and R_(6a) is hydrogen, methyl, methoxy, acetamido or --NHCONH₂ ; ##STR296## in which Y_(a) is as defined above and R₄ is hydrogen or sulpho; K_(a) is one of the radicals (k₁ ') to (k₄ '), ##STR297## in which R_(1b), R₄, Y_(a), Hal, W_(1b) and Z_(a) ' are as defined above, b is 0 or 1; R_(7a) is ##STR298## wherein R₄, Y_(a), b and r are as defined above, R_(8a) is hydrogen, methyl, methoxy, chloro or sulpho, R_(9a) is hydrogen, methyl, methoxy or chloro; R_(10a) is methyl or --CH₂ SO₃ H, R_(11a) is hydrogen, --CONH₂, sulpho, --CH₂ SO₃ H or --CH₂ --Y_(a), wherein Y_(a) is as defined above, R_(12b) is hydrogen, methyl, ethyl, cyclohexyl or --C₁₋₄ alkylene-E_(a), wherein E_(a) is carboxy, sulpho, --OSO₃ H, hydroxy or --NR_(19a) R_(20a), in which each of R_(19a) and R_(20a) is independently hydrogen, methyl, ethyl, 2-hydroxyethyl or phenyl(C₁₋₂ alkyl), or --NR_(19a) R_(20a) is piperidino, morpholino or piperazino, R_(8a) and R_(9a) are as defined above, R₁₃ is hydroxy or --NH₂, R_(14a) is methyl or carboxy; R_(15a) is hydrogen, methyl or methoxy, and R_(16a) is hydrogen, methyl, methoxy, acetamido or --NHCONH₂ ;in which compounds of formula Ia the same provisos (i) to (v) set forth in claim 1 for compounds of formula I apply accordingly.
 10. A compound according to claim 1, which corresponds to formula Ib ##STR299## or salts thereof, in which D_(b) is one of the radicals (d₂ ') to (d₄ ') or (d₆ ') or (d₇ '), ##STR300## wherein R_(2a) is hydrogen, methyl, methoxy or sulpho,R_(3b) is hydrogen, methyl or methoxy, R₄ is hydrogen or sulpho, q is 1 or 2, a is 0 or 1, andeach Y_(a) is --NR_(1b) -Z_(a) ' or ##STR301## in which each R_(1b) is independently hydrogen or methyl, Hal is fluoro or chloro, W_(1b) is --NR_(1b) --B_(1b) --NR_(1b) -- or ##STR302## wherein B_(1b) is linear or branched C₂₋₃ alkylene, --CH₂ CH(OH)CH₂ -- or ##STR303## and R_(17b) is hydrogen or sulpho; and Z_(a) ' is ##STR304## wherein T₁ ' is hydrogen or chloro; ##STR305## in which r is 2 or 3 and the substituents are in the following positions: a) when the azo group is in the 1-position and r is 2, the sulpho groups are in the 3,6-; 3,8-; 4,6- or 4,8-positions; b) when the azo group is in the 1-position and r is 3, the sulpho groups are in the 3,6,8-positions; c) when the azo group is in the 2-position and r is 2, the sulpho groups are in the 1,5-; 3,6-; 4,8-; 5,7- or 6,8-positions; d) when the azo group is in the 2-position and r is 3, the sulpho groups are in the 3,6,8- or 4,6,8-positions; ##STR306## in which r is 2 or 3 and the sulpho groups in the naphthyl ring are in the same positions as shown for (d₃ ') above, R_(5a) is hydrogen, methyl or methoxy, and R_(6a) is hydrogen, methyl, methoxy, acetamido or --NHCONH₂ ; ##STR307## in which each R_(1b) and Z_(a) ' is as defined above, X₁ ' is ##STR308## wherein R_(1b) is as defined above and the marked carbon atom is attached to the azo group; and X₂ ' is ##STR309## wherein R_(1b) is as defined above and the marked carbon atom is attached to the Z_(a) '-NR_(1b) -group; R_(14a) is methyl or carboxy, R_(18a) is hydrogen, chloro, methyl or methoxy, p' is 1 or 2, and R_(1b) and Z_(a) ' are as defined above;with the proviso that i) when D_(b) is one of the radicals (d₂ ') to (d₄ '), at least one Z_(a) ' is ##STR310## and ii) when two radicals Z_(a) ' are present, these are identical.
 11. A compound according to claim 10, in which R_(14a) is carboxy, R_(18a) is hydrogen, p' is 1 and each R_(1b) is hydrogen.
 12. A compound according to claim 10, which corresponds to formula Ic, ##STR311## or salts thereof, in which D_(c) is one of the radicals (d₆ ") and (d₇ ") ##STR312## wherein X₁ " is ##STR313## in which the marked carbon atom is attached to the azo group; X₂ " is ##STR314## in which the marked carbon atom is attached to the Z_(a) '-NH-group; each Z_(a) ' is as defined in claim 11 and the two groups Z_(a) ' are the same.
 13. A process for dyeing or printing a hydroxy group- or nitrogen-containing organic substrate comprising applying to the substrate a compound of formula I according to claim 1, or a mixture thereof.
 14. A process according to claim 13, wherein the substrate is a fibre material comprising natural or regenerated cellulose.
 15. A compound according to claim 1 wherein D is one of the radicals (d₂) to (d₅).
 16. A compound according to claim 15 wherein K is (k₃).
 17. A compound according to claim 1 wherein D is one of the radicals (d₆) or (d₇). 